Verhopäällystyspastojen analyysimenetelmät

Diplomityön tarkoitus oli selvittää verhopäällystyspastoille sopivia analyysimenetelmiä. Verhopäällystyksessä onnistunut päällystystapahtuma vaatii venymäviskositeetin ja pintajännityksen hyvää hallintaa. Kirjallisuusosassa käsiteltiin verhopäällystystä, verhopäällystyspastojen koostumusta, reologiaa ja pintajännitystä. Kirjallisuusosassa käsiteltiin lisäksi verhopäällystyspastojen reologian ja pintajännityksen mittaamiseen soveltuvia mittausmenetelmiä. Verhopäällystyksen luonteen vuoksi kirjallisuusosassa syvennyttiin venymäviskositeetin ja dynaamisen pintajännityksen mittaamiseen tarkoitettuihin menetelmiin. Kokeellisessa osassa tutkittiin päällystyspastasarjojen reologiaa ja pintajännitystä verhopäällystystä varten. Osaan päällystyspastoista luotiin venymäviskositeettia ja osasta laskettiin pintajännitystä. Venymäviskositeetin mittaamista varten työssä käytettiin ACAV A2 -reometriin liitettyjä teräsreikälevyjä. Dynaamisen pintajännityksen mittaamista varten työssä käytettiin KSV BPA-800P -pintajännitysmittaria. ACAV A2 -reometriin liitettyjen teräsreikälevyjen (reiän sisähalkaisija 0,5 tai 0,7 mm) avulla mitattiin venymäviskositeettia kuvaavia Eulerin lukuarvoja onnistuneesti suurilla kiintoainepitoisuuksilla (50, 60 tai 65 p %). Erikoispaksuntajan määrää lisäämällä onnistuttiin luomaan huomattavaa venymäviskositeettia. Kiintoainepitoisuuden kasvaessa kasvoi myös venymäviskositeetti. Tavanomaisille paksuntajille mitattiin hieman kohonneita venymäviskositeetteja verrattuna referenssipäällystyspastaan. Pigmenttikoostumuksella (kalsiumkarbonaatti/kaoliini) ei näyttänyt olevan vaikutusta venymäviskositeettiin, tai vaikutus oli suhteellisen pieni. Dynaamisen pintajännityksen mittaamista varten käytössä ollut KSV BPA-800P -pintajännitysmittari ei toiminut luotettavasti, vaikka näytteitä laimennettiin. Kiintoainepitoisuudessa 10 p-% olleilla laimennoksilla saavutettiin analysoinnin kannalta parhaat tulokset. Tuloksista saatiin kuitenkin viitteitä, että kyseinen mittari voisi olla potentiaalinen menetelmä dynaamisen pintajännityksen mittaamiseksi.

Käytetyn voiteluöljyn regenerointilaitoksen prosessivesien karakterisointi

Käytetyn voiteluöljyn regeneroinnissa muodostuu prosessivettä useista lähteistä. Tehokas päästöjenhallinta on yksi tärkeimmistä tavoitteista regenerointilaitoksen operoinnissa ja sen takia sitä tulee kehittää jatkuvasti entistä paremmaksi. Tavoitteisiin pääsemiseksi on oleellista tunnistaa vesienkäsittelyprosessin laadullinen massatase ja laadunvaihtelut ajotilanteiden mukaan. Työssä tutkitaan ja analysoidaan veden sisältämiä epäpuhtauksia sekä kirjallisuuslähteiden perusteella, että standardimenetelmillä ja modifioiduilla menetelmillä, joilla on akkreditointi. Analyysituloksista muodostetaan laadullinen massatase, josta nähdään epäpuhtauksien ja niitä kuvaavien parametrien kuormitukset kussakin prosessivesivirrassa. Tulosten perusteella arvioidaan nykyisen vesienkäsittelyn tehokkuutta, sen säätömahdollisuuksia ja kehitystarvetta. Tarkastelun ulkopuolelle kuitenkin jätetään vesienkäsittelystä ulosjohdettavan prosessiveden puhdistuslaitos. Tutkimusten perusteella regenerointilaitoksessa muodostuvien prosessivesien epäpuhtaudet koostuvat öljystä, BTEX-yhdisteistä, fenoliyhdisteistä, liuottimista, polttoaineiden ja voiteluöljyjen lisäaineista, typpi- ja rikkiyhdisteistä, metalliyhdisteistä sekä kiintoaineesta. Öljy jakautuu kevyisiin (C5-C10), keskiraskaisiin (C10-21) ja raskaisiin (C21-40) jakeisiin. Vesienkäsittelyssä suurin osa öljystä ja epäpuhtauksista saadaan erottumaan vedestä, jolloin puhdistuslaitokselle päätyy jäämäpitoisuudet öljyä, haihtuvia yhdisteitä sekä muita epäpuhtauksia. Puhdistuslaitosta kuormittavat eniten liuenneet orgaaniset yhdisteet sekä korkeaa kemiallista hapenkulutusta aiheuttavat epäorgaaniset yhdisteet (suolat), joiden erottamista prosessivesistä on syytä tulevaisuudessa kehittää.

Enhanced muscle strength with carbohydrate supplement two hours before open cholecystectomy: a randomized, double-blind study

Objective: to investigate the effects of preoperative fasting abbreviation with oral supplementation with carbohydrate in the evolution of grip strength in patients undergoing cholecystectomy by laparotomy. Methods : we conducted a clinical, randomizeddouble blind study with adult female patients, aged 18-60 years. Patients were divided into two groups: Control Group, with fasting prescription 6-8h until the time of operation; and Intervention Group, which received prescription of fasting for solids 6-8h before surgery, but ingested an oral supplement containing 12.5% carbohydrate, six (400ml) and two (200ml) hours before theprocedure. The handgrip strength was measured in both hands in both groups, at patient's admission (6h before surgery), the immediate pre-operative time (1h before surgery) and 12-18h postoperatively. Results : we analyzed 27 patients, 14 in the intervention group and 13 in the control group. There was no mortality. The handgrip strength (mean [standard deviation]) was significantly higher in the intervention group in the three periods studied, in at least one hand: preoperatively in the dominant hand (27.8 [2.6] vs 24.1 [3.7] kg; p=0.04), in the immediate preoperative in both hands, and postoperatively in the non-dominant hand (28.5 [3.0] vs 21.3 [5.9] kg; p=0.01). Conclusion : the abbreviation of preoperative fasting to two hours with drink containing carbohydrate improves muscle function in the perioperative period.

Sellutehtaan vedenkäytön vähentäminen

Työn tarkoituksena oli etsiä mahdollisia kohteita sellutehtaan veden käytön vähen-tämiseksi. Analyysien avulla selvitettiin voidaanko havaittujen kohteiden tällä hetkellä menetettyjä vesivirtoja käyttää uudelleen. Lopuksi arvioitiin miten kierrä-tettävät vedet vaikuttaisivat raakaveden laatuun, mikäli ne yhdistettäisiin tämän joukkoon. Veden käytön vähentämiskohteita etsittiin tutkimalla tehtaan prosessi-kaavioita osastokohtaisesti sekä selvittämällä näin havaittuja kohteita osastoilla. Työn kokeellinen osa koostui vesianalyyseistä. Vesianalyyseissä määritettiin seu-raavat arvot sellutehtaalle tulevasta vedestä: sameus (FTU), kiintoaine, sähkönjoh-tavuus, pH, CODCr, BOD7ATU, kokonaisfosfori P, Mn, Cl, K, Ca, Mg ja AOX. Nämä tehtiin valituista kohteista havaituista tällä hetkellä tehtaalta pois johdetuista mutta mahdollisesti kierrätettävistä vesistä. Työn tuloksien perusteella havaittiin, että seuraavissa tarkasteluun valituissa koh-teissa vedet olivat hyvin puhtaita ja talteen otettavia kierrätykseen. Näitä olivat savukaasupesurin vedet, sekundäärilauhdesäiliön vedet sekä tiivistevedet. Haih-duttamon lämminvesisäiliön sekä kuivauskone 4 kiertovesitornin vedet olivat hieman likaantuneet mutta hyvin kierrätettävissä. Koivulinjan D0-vaiheen, havu-linjan D1-vaiheen sekä kuivauskone 4 lajittamon vesivirtoja ei likaantumisen vuoksi kannattanut kerätä hyötykäyttöön.

Analysis and validation of space averaged drag model for numerical simulations of gas-solid flows in fluidized beds

This thesis presents an approach for formulating and validating a space averaged drag model for coarse mesh simulations of gas-solid flows in fluidized beds using the two-fluid model. Proper modeling for fluid dynamics is central in understanding any industrial multiphase flow. The gas-solid flows in fluidized beds are heterogeneous and usually simulated with the Eulerian description of phases. Such a description requires the usage of fine meshes and small time steps for the proper prediction of its hydrodynamics. Such constraint on the mesh and time step size results in a large number of control volumes and long computational times which are unaffordable for simulations of large scale fluidized beds. If proper closure models are not included, coarse mesh simulations for fluidized beds do not give reasonable results. The coarse mesh simulation fails to resolve the mesoscale structures and results in uniform solids concentration profiles. For a circulating fluidized bed riser, such predicted profiles result in a higher drag force between the gas and solid phase and also overestimated solids mass flux at the outlet. Thus, there is a need to formulate the closure correlations which can accurately predict the hydrodynamics using coarse meshes. This thesis uses the space averaging modeling approach in the formulation of closure models for coarse mesh simulations of the gas-solid flow in fluidized beds using Geldart group B particles. In the analysis of formulating the closure correlation for space averaged drag model, the main parameters for the modeling were found to be the averaging size, solid volume fraction, and distance from the wall. The closure model for the gas-solid drag force was formulated and validated for coarse mesh simulations of the riser, which showed the verification of this modeling approach. Coarse mesh simulations using the corrected drag model resulted in lowered values of solids mass flux. Such an approach is a promising tool in the formulation of appropriate closure models which can be used in coarse mesh simulations of large scale fluidized beds.

Breed and season influence on milk quality parameters and in mastitis occurrence

The aims of the present study were to evaluate the performance of Jersey and Holstein cows under different rainfall conditions (dry and rainy seasons) by monitoring aspects related to subclinical mastitis (somatic cell count, microbiological isolation, type of isolated pathogen), milk quality (lactose, protein, fat, total solids) and production (mean milk production) of both breeds. The study was carried out in a dairy farm located in the state of São Paulo, Brazil. Eight visitations were done to the farm, four in a period of high rainfall and four in a period of low rainfall. Milk samples were collected from 79 Holstein cows and 37 Jersey cows for electronic somatic cell count and determination of the main milk components (protein, fat, total solids, lactose). Milk fat, protein, total solids and production were influenced by breed and the season, with similar tendencies for both breeds in both seasons. Somatic cell count (SCC) showed similar results for both breeds. Holstein cows with intramammary infections (IMI) presented a higher increase in SCC when compared to Jersey cows (P<0.001). In the dry season, 53 animals had IMI in at least one month during the study, which 32 were Holstein and 21 were Jersey cows. In the rainy season, 65 animals had intramammary infection, being 43 Holstein and 22 Jersey cows. The frequency of IMI cases was larger in the rainy season than in the dry season. Jersey cows had a lower chance of showing IMI signs and symptoms than Holstein cows in the rainy season (odds ratio=0.52). The larger number of IMI cases in the rainy season may have led to a lower milk lactose rate for both breeds, thus milk lactose rate can be considered an indicator of IMI status. There was prevalence of contagious pathogens overall in the study. The applied model showed that environmental pathogens were more frequently isolated from the breed Jersey, regardless of the study season. There seems to be differences in the immune response of Jersey and Holstein breeds.

Enteral fluid therapy through nasogastric tube in rumen cannulated goats

This paper reports the effects of fluid therapy in goats through nasogastric route with an electrolyte solution composed by concentrations of sodium, potassium and chloride similar to goat plasma (140mmol/L of Na+, 4.5mmol/L of K+, 110mmol/L of Cl-). Four Alpine Chamoisee goats, two of them with evident leakage of the rumen cannulas, were used in a crossover experimental design of two periods and two groups. In one group the two goats were submitted to a treatment protocol to induce dehydration before the fluid therapy, whereas the other group was not. Fluid therapy consisted supplying 10mL/kg/h of the electrolyte solution during 8 hours. No signs of discomfort or stress were observed. The dehydration model employed caused a mild dehydration indicated by decrease in feces humidity, body weight and abdominal circumference, and increase in plasma total solids concentration. During fluid therapy globular volume and plasma total solids decreased, whereas % body weight and abdominal circumference increased. No signs of hyperhydration were observed and serum electrolytes (Na+, Cl-, K+) presented no significant alterations in both groups. Fluid therapy proposed in this study was efficient to treat dehydration, even for rumen cannulated animals with evident leakage, and can be administrated safely with no electrolyte imbalance.

Extraction of polymeric galactoglucomannans from spruce wood by pressurized hot water

The major type of non-cellulosic polysaccharides (hemicelluloses) in softwoods, the partly acetylated galactoglucomannans (GGMs), which comprise about 15% of spruce wood, have attracted growing interest because of their potential to become high-value products with applications in many areas. The main objective of this work was to explore the possibilities to extract galactoglucomannans in native, polymeric form in high yield from spruce wood with pressurised hot-water, and to obtain a deeper understanding of the process chemistry involved. Spruce (Picea abies) chips and ground wood particles were extracted using an accelerated solvent extractor (ASE) in the temperature range 160 – 180°C. Detailed chemical analyses were done on both the water extracts and the wood residues. As much as 80 – 90% of the GGMs in spruce wood, i.e. about 13% based on the original wood, could be extracted from ground spruce wood with pure water at 170 – 180°C with an extraction time of 60 min. GGMs comprised about 75% of the extracted carbohydrates and about 60% of the total dissolved solids. Other substances in the water extracts were xylans, arabinogalactans, pectins, lignin and acetic acid. The yields from chips were only about 60% of that from ground wood. Both the GGMs and other non-cellulosic polysaccharides were extensively hydrolysed at severe extraction conditions when pH dropped to the level of 3.5. Addition of sodium bicarbonate increased the yields of polymeric GGMs at low additions, 2.5 – 5 mM, where the end pH remained around 3.9. However, at higher addition levels the yields decreased, mainly because the acetyl groups in GGMs were split off, leading to a low solubility of GGMs. Extraction with buffered water in the pH range 3.8 – 4.4 gave similar yields as with plain water, but gave a higher yield of polymeric GGMs. Moreover, at these pH levels the hydrolysis of acetyl groups in GGMs was significantly inhibited. It was concluded that hot-water extraction of polymeric GGMs in good yields (up to 8% of wood) demands appropriate control of pH, in a narrow range about 4. These results were supported by a study of hydrolysis of GGM at constant pH in the range of 3.8 – 4.2 where a kinetic model for degradation of GGM was developed. The influence of wood particle size on hot-water extraction was studied with particles in the range of 0.1 – 2 mm. The smallest particles (< 0.1 mm) gave 20 – 40% higher total yield than the coarsest particles (1.25 – 2 mm). The difference was greatest at short extraction times. The results indicated that extraction of GGMs and other polysaccharides is limited mainly by the mass transfer in the fibre wall, and for coarse wood particles also in the wood matrix. Spruce sapwood, heartwood and thermomechnical pulp were also compared, but only small differences in yields and composition of extracts were found. Two methods for isolation and purification of polymeric GGMs, i.e. membrane filtration and precipitation in ethanol-water, were compared. Filtration through a series of membranes with different pore sizes separated GGMs of different molar masses, from polymers to oligomers. Polysaccharides with molar mass higher than 4 kDa were precipitated in ethanol-water. GGMs comprised about 80% of the precipitated polysaccharides. Other polysaccharides were mainly arabinoglucuronoxylans and pectins. The ethanol-precipitated GGMs were by 13C NMR spectroscopy verified to be very similar to GGMs extracted from spruce wood in low yield at a much lower temperature, 90°C. The obtained large body of experimental data could be utilised for further kinetic and economic calculations to optimise technical hot-water extractionof softwoods.

Gas-solid two-phase flow in the riser of circulating fluidized beds: mathematical modelling and numerical simulation

A mathematical model is developed for gas-solids flows in circulating fluidized beds. An Eulerian formulation is followed based on the two-fluids model approach where both the fluid and the particulate phases are treated as a continuum. The physical modelling is discussed, including the formulation of boundary conditions and the description of the numerical methodology. Results of numerical simulation are presented and discussed. The model is validated through comparison to experiment, and simulation is performed to investigate the effects on the flow hydrodynamics of the solids viscosity.

Detection of Illicit Drugs and Drug Precursors with Cantilever-Enhanced Photoacoustic Spectroscopy

In this study, cantilever-enhanced photoacoustic spectroscopy (CEPAS) was applied in different drug detection schemes. The study was divided into two different applications: trace detection of vaporized drugs and drug precursors in the gas-phase, and detection of cocaine abuse in hair. The main focus, however, was the study of hair samples. In the gas-phase, methyl benzoate, a hydrolysis product of cocaine hydrochloride, and benzyl methyl ketone (BMK), a precursor of amphetamine and methamphetamine were investigated. In the solid-phase, hair samples from cocaine overdose patients were measured and compared to a drug-free reference group. As hair consists mostly of long fibrous proteins generally called keratin, proteins from fingernails and saliva were also studied for comparison. Different measurement setups were applied in this study. Gas measurements were carried out using quantum cascade lasers (QLC) as a source in the photoacoustic detection. Also, an external cavity (EC) design was used for a broader tuning range. Detection limits of 3.4 particles per billion (ppb) for methyl benzoate and 26 ppb for BMK in 0.9 s were achieved with the EC-QCL PAS setup. The achieved detection limits are sufficient for realistic drug detection applications. The measurements from drug overdose patients were carried out using Fourier transform infrared (FTIR) PAS. The drug-containing hair samples and drug-free samples were both measured with the FTIR-PAS setup, and the measured spectra were analyzed statistically with principal component analysis (PCA). The two groups were separated by their spectra with PCA and proper spectral pre-processing. To improve the method, ECQCL measurements of the hair samples, and studies using photoacoustic microsampling techniques, were performed. High quality, high-resolution spectra with a broad tuning range were recorded from a single hair fiber. This broad tuning range of an EC-QCL has not previously been used in the photoacoustic spectroscopy of solids. However, no drug detection studies were performed with the EC-QCL solid-phase setup.

Käänteisosmoosin esikäsittelymenetelmät

Käänteisosmoosisuodatusta käytetään erityisesti teollisuuden jätevesien loppupuhdistuksessa. Suodatuksen ongelmana on kalvojen likaantuminen ja tukkiutuminen. Tässä työssä on aiempia tutkimuksia hyväksikäyttäen tutkittu käänteisosmoosiin tulevan veden esikäsittelemistä niin, että kalvojen likaantumiselta vältyttäisiin. Menetelmien vertailussa on käytetty erilaisia veden laadusta kertovia parametreja. Ongelmallisimmiksi aineksiksi huomattiin orgaaninen aines ja jotkin veteen liuenneet ionit. Kiintoaineen erottaminen ei ole ollut suuri ongelma, sillä sen saa poistettua tavallisesti käytetyillä rakeissuodatuksella, laskeutuksella, flotaatiolla ja kalvosuodatuksella. Orgaanista ainesta on saatu erotettua erityisesti hapettamalla, aktiivilieteprosessilla ja biologisella aktiivihiilisuodattimella. Mikro- ja ultrasuodatusta käytetään usein juuri ennen käänteisosmoosia poistamaan erityisesti kolloidista materiaalia ja joitain liuenneita ioneja. Flokkien muodostaminen koagulaatiossa ja flokkulaatiossa parantaa lähes kaikkien menetelmien toimivuutta selvästi. Veden puhdistuksessa käytetyt kemikaalit voivat myös liika-annosteltuina liata kalvoja. Vesien pitoisuuksissa eri ainesten osalta on huomattavia eroja, joten puhdistettava vesi on hyvä analysoida etukäteen parhaiden käsittelymenetelmien valitsemiseksi.

Pressure filtration characteristics of enzymatically hydrolyzed biomass suspensions

Enzymatic hydrolysis of lignocellulosic polymers is likely to become one of the key technologies enabling industrial production of liquid biofuels and chemicals from lignocellulosic biomass. Certain types of enzymes are able to hydrolyze cellulose and hemicellulose polymers to shorter units and finally to sugar monomers. These monomeric sugars are environmentally acceptable carbon sources for the production of liquid biofuels, such as bioethanol, and other chemicals, such as organic acids. Liquid biofuels in particular have been shown to contribute to the reduction of net emissions of greenhouse gases. The solid residue of enzymatic hydrolysis is composed mainly of lignin and partially degraded fibers, while the liquid phase contains the produced sugars. It is usually necessary to separate these two phases at some point after the hydrolysis stage. Pressure filtration is an efficient technique for this separation. Solid-liquid separation of biomass suspensions is difficult, because biomass solids are able to retain high amounts of water, which cannot be readily liberated by mechanical separation techniques. Most importantly, the filter cakes formed from biomaterials are compressible, which ultimately means that the separation may not be much improved by increasing the filtration pressure. The use of filter aids can therefore facilitate the filtration significantly. On the other hand, the upstream process conditions have a major influence on the filtration process. This thesis investigates how enzymatic hydrolysis and related process conditions affect the filtration properties of a cardboard suspension. The experimental work consists of pressure filtration and characterization of hydrolysates. The study provides novel information about both issues, as the relationship between enzymatic hydrolysis conditions and subsequent filtration properties has so far not been considered in academic studies. The results of the work reveal that the final degree of hydrolysis is an important factor in the filtration stage. High hydrolysis yield generally increases the average specific cake resistance. Mixing during the hydrolysis stage resulted in undefined changes in the physical properties of the solid residue, causing a high filtration resistance when the mixing intensity was high. Theoretical processing of the mixing data led to an interesting observation: the average specific cake resistance was observed to be linearly proportional to the mixer shear stress. Another finding worth attention is that the size distributions of the solids did not change very dramatically during enzymatic hydrolysis. There was an observable size reduction during the first couple of hours, but after that the size reduction was minimal. Similarly, the size distribution of the suspended solids remained almost constant when the hydrolyzed suspension was subjected to intensive mixing. It was also found that the average specific cake resistance was successfully reduced by the use of filter aids. This reduction depended on the method of how the filter aids were applied. In order to obtain high filtration capacity, it is recommended to use the body feed mode, i.e. to mix the filter aid with the slurry prior to filtration. Regarding the quality of the filtrate, precoat filtration was observed to produce a clear filtrate with negligible suspended solids content, while the body feed filtrates were turbid, irrespective of which type of filter aid was used.

Turbulenssimallien soveltuminen syklonien numeeriseen virtauslaskentaan

Tässä työssä tutkittiin miten totuudenmukaisia tuloksia syklonierottimen virtauskentästä saadaan numeerisella laskennalla, kun käytetään eri turbulenssimalleja. Tarkoitus oli myös selvittää yleisesti syklonin toimintaperiaatteita, haasteita sen käytössä sekä syklonin numeerisen virtauslaskennan perusteita. Numeerisen virtauslaskennan teoria selitetään pääpiirteittäin, samoin turbulenssin mallinnus. Työn laskentaosiossa simuloitiin Fluent-ohjelmalla syklonin virtauskenttää kuumalla ilmalla sekä kahdella eri turbulenssimallilla ja verrattiin tuloksia kirjallisuudesta löytyviin mittaustuloksiin. Simuloinnit suoritettiin sekä ajasta riippuvana että ajasta riippumattomana ja kahdella eri laskentahilalla. Simulointien tulokset osoittivat, että RNG k-ε turbulenssimalli ei kykene tuottamaan totuu-denmukaista virtauskenttää. Toisen käytetyn turbulenssimallin, Reynolds-jännitysmallin tulokset vastasivat enemmän mittaustuloksia. Reynolds-jännitysmallia voidaan pitää käyttökelpoisena syklonin simuloinnissa tämän työn ja kirjallisuuden perusteella. Mallissa oli yksinkertaistuksia, esimerkiksi kiinteää ainetta ei otettu huomioon lainkaan.

QUALITY OF PROCESSING TOMATO FRUITS IN COMPETITION WITH Solanum americanum

ABSTRACT Five experiments were conducted to evaluate the hypothesis that Solanum americanum density and time of coexistence affect the quality of processing tomato fruit. The tomato crop was established using either the direct drilling or the transplanting technique. The factors evaluated consisted of weed density (from 0 up to 6 plants m-2) and time of weed interference (early bloom stage, full flowering stage, fruit filling, and harvest time). The effects of competition on tomato fruit quality were analysed using a multiple model. Tomato variables evaluated included industrial fruit types (which depended on ripeness and disease infection) and soluble solids level(obrix). Tomato fruit quality is dependent on the factors tested. Under low densities (< 6 plants m-2) of S. americanum there was a small impact on the quality of the tomato fruits. The percentage of grade A (mature fruit with red color and without pathogen infection) tomato fruits is the variable most affect by the independent variables. The impact of these independent variables on the percentage of grade C (green and/or with more than 15% disease infection) tomato yield was of smaller magnitude and in an inverse trend as the observed for grade A. The level of soluble solids was influenced by the weed interference on only two experiments, but the impact was of small magnitude. The impact of the results on current and future crop management practices is discussed.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.